CN113004344B - Preparation method of methyl seleno-glucose and selenocarbon - Google Patents
Preparation method of methyl seleno-glucose and selenocarbon Download PDFInfo
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- C07H1/00—Processes for the preparation of sugar derivatives
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Abstract
A method for preparing methyl seleno-glucose and selenocarbon belongs to the technical field of material production. Mixing glucose and methyl selenium magnesium in a solvent for reaction, and evaporating the solvent to obtain methyl seleno glucose; and mixing and grinding methyl seleno-glucose and potassium bromide, calcining in a nitrogen atmosphere, cooling to room temperature, grinding, washing with deionized water, centrifuging, precipitating, and drying to obtain the selenium carbon. The invention takes cheap and easily available glucose as a main material, and prepares the methyl seleno-glucose with better stability by evaporating the solvent after reacting with the methyl magnesium selenide. In the methyl seleno-glucose, the introduction of methyl makes the selenium functional group more stable, and is difficult to be oxidized and decomposed, so that the selenium-containing fertilizer is more practical as a leaf surface selenium fertilizer. On the basis, the selenium carbon with higher catalytic activity is prepared and used for catalyzing molecular oxygen to oxidize beta-ionone to synthesize useful epoxide.
Description
Technical Field
The invention belongs to the technical field of material production.
Background
The selenium-containing material developed by taking the sugar as the carrier has the advantages of cheap and easily obtained raw materials, biocompatibility and the like. The inventors have conducted long-term studies on this, and have developed selenoglucose, which can be further calcined to prepare a selenocarbon catalyst material (Catal. Sci. Technol., 2018, 85017), the related art has been granted patent protection (a method for synthesizing nano-selenium material as disclosed in ZL 201610899676.8), and selenoglucose has been produced in kilogram scale (Ind. Eng. Chem. Res. 2020, 59, 10763) And is widely used as a selenium-rich foliar fertilizer.
However, the prior art has some problems. The biggest problem is thatThe prepared seleno-glucose is unstable, is easily oxidized and discolored by air in aqueous solution and is rapidly decomposed, thereby influencing the effect (seeInd. Eng. Chem. Res. 2020, 59, 10763 article fig. 1). The selenium-rich foliar fertilizer developed in the technology needs to be used quickly after being prepared into an aqueous solution, is difficult to be simultaneously scattered with a plurality of pesticides, needs to be independently fertilized, and increases the labor cost. In addition, the selenium carbon material fired with this selenoglucose has poor catalytic activity, and requires the use of a strong oxidizing agent such as hydrogen peroxide (C) in the catalytic oxidation reactionCatal. Sci. Technol., 2018, 85017), thereby increasing the reaction cost and being not safe enough. Therefore, the stable selenoglucose and the selenocarbon material with higher reaction activity are developed, the problems can be solved, and the method has good practical application value.
Disclosure of Invention
In view of the above defects of the prior art, the present invention aims to provide a method for preparing methylselenoclucose and selenocarbon, so as to make methylselenoclucose more stable and selenocarbon more active.
The technical scheme of the invention is as follows: mixing glucose and methyl selenium magnesium in a solvent for reaction, and then evaporating the solvent to dryness to obtain methyl seleno-glucose; mixing and grinding methyl seleno-glucose and potassium bromide, calcining in nitrogen atmosphere, cooling to room temperature, grinding, washing with deionized water, centrifuging to obtain precipitate, and drying in an oven to obtain selenium carbon.
The invention takes cheap and easily available glucose as a main material, and prepares the methyl seleno-glucose with better stability by evaporating the solvent after reacting with the methyl magnesium selenide. In the methyl seleno-glucose, the introduction of methyl makes the selenium functional group more stable, thereby being difficult to be oxidized and decomposed and being more practical as the foliar selenium fertilizer. On the basis, the selenium carbon with higher catalytic activity is prepared and used for catalyzing molecular oxygen to oxidize beta-ionone to synthesize useful epoxide.
In the invention, the methyl magnesium selenide can be prepared by reacting selenium powder with methyl magnesium bromide (namely, a Grignard reagent which can be directly purchased or prepared by a known method). Wherein the molar ratio of the selenium powder to the methyl magnesium bromide is 0.9: 1 (the Grignard reagent is slightly excessive, so that the selenium powder is fully utilized).
In the invention, the solvent is added into the obtained methyl magnesium selenide solution for dilution, then glucose is added for reaction, and the dry powder of the methyl glucose selenide can be obtained after the solvent is evaporated to dryness. The powder can be calcined to prepare the selenium carbon.
In the invention, the feeding molar ratio of the glucose to the methyl selenium magnesium is 2-8: 1, preferably 5: 1. In this ratio, the methyl selenium can be promoted to be fully absorbed by glucose, and the selenium carbon prepared by further calcining has higher catalytic activity.
In the invention, the reaction temperature condition of the glucose and the methyl selenium magnesium is 20-80 ℃, and preferably 50 ℃. At this temperature, the methyl selenium magnesium reacts with glucose most fully, but not too high to cause side reaction, so that the selenium carbon further fired has the highest catalytic activity.
In the invention, when the corresponding selenium and carbon is prepared, the calcination temperature is 400-600 ℃, and preferably 500 ℃; the time is 2-5 h, preferably 3 h. Calcination at this temperature and time can achieve sufficient carbonization without causing decomposition of the material due to excessive calcination. So that the catalyst activity can be maintained well.
In addition, the mixing mass ratio of the methyl seleno-glucose to the potassium bromide is 1: 10. The material prepared by the proportion can fully utilize the template effect of the potassium bromide to generate enough reaction sites, and the loss of selenium during calcination due to the fact that the material is too loose because of the excessive use of the potassium bromide is avoided.
The tetrahydrofuran or anhydrous ether.
Drawings
FIG. 1 is an aqueous solution of methylselenochloroglucose exposed to air for 20 days.
FIG. 2 is the X-ray photoelectron spectrum (XPS spectrum for short) of newly prepared methylseleno glucose.
FIG. 3 is the X-ray photoelectron spectrum (XPS spectrum for short) of methylseleno glucose as water solution after being exposed in air for 31 days.
Detailed Description
Firstly, preparing methylseleno glucose:
1. putting 1.42 g (18 mmol) of selenium powder and a magnetic stirrer into a 250 mL three-necked bottle, vacuumizing for replacing nitrogen for 3-4 times, and placing in an ice water bath.
2. Slowly injecting methyl magnesium bromide (1 mol/L, 20 mL and 20 mmol of methyl magnesium bromide) into the three-mouth bottle by using a syringe under the stirring state, stirring and reacting for 1h, removing the ice water bath, and continuing to react for 1h at room temperature to obtain the methyl selenium magnesium.
3. Adding 16.2 g (90 mmol) of glucose powder into the three-mouth bottle in three times, and adding the glucose powder again after the glucose powder is added last time and stirred uniformly each time.
4. Sealing the three-necked flask, heating to react at 50 ℃ for 4h, then turning off the heating and continuing stirring, then adding 30mL of anhydrous ether or tetrahydrofuran, stirring at room temperature for 12h, and then spin-drying the solvent at 50 ℃ by using a rotary evaporator to obtain the methyl seleno-glucose dry powder.
The content of selenium in the methyl seleno-glucose dry powder is 6.6 wt% by the measurement of inductively coupled plasma mass spectrometry (ICP-MS).
II, preparing selenium and carbon:
mixing 1g of methyl seleno-glucose dry powder with 10g of potassium bromide, grinding in a mortar for about 10min until the powder is uniformly mixed, transferring the mixture into a ceramic cup to be covered, firing in a tube furnace at 500 ℃ in a nitrogen atmosphere for 3h, naturally cooling to room temperature, grinding the obtained solid again, washing with deionized water for 3-4 times, centrifuging, removing supernatant, and finally drying in an oven at 105 ℃ to obtain the selenium carbon.
The selenium content in the selenium carbon is 7.8 wt% measured by ICP-MS.
The medicines used in the preparation process are as follows:
| name of medicine | Content (wt.) | CAS number | Production trade company |
| Methyl magnesium bromide | 1.0mol/L in THF | 75-16-1 | Saen chemical technology (Shanghai) Co., Ltd |
| Selenium powder | 99.99% | 7782-49-2 | Shanghai Yixue chemical Co Ltd |
| D- (+) -glucose | 99% | 50-99-7 | Saen chemical technology (Shanghai) Co., Ltd |
| Anhydrous diethyl ether | ≥99.7% | 60-29-7 | China east China pharmaceutical Co Ltd |
| Potassium bromide | ≥99.0 | 7758-02-3 | SINOPHARM CHEMICAL REAGENT Co.,Ltd. |
Thirdly, testing the catalytic activity of the selenium and carbon:
taking a 35 mL test tube, adding 20mg of selenium-carbon and 10 percent of selenium-carbonN-hydroxyphthalimide and a magneton, vacuum-pumping, and introducing oxygen. Then 1 mL of 1.4-dioxane and 1mmol of beta-ionone are respectively added into the system by a syringe to react for 24 h at the temperature of 80 ℃, and after the reaction is finished, the product is obtained by column chromatography separation (the developing solvent is formed by mixing petroleum ether and ethyl acetate in the volume ratio of 40: 1).
Through the above test of selenium carbon catalyzed beta-ionone oxidation, the results show that: under the catalysis of selenium carbon, beta-ionone is oxidized to generate epoxy ionone, and the yield is 52%.
The drugs used in the experiment were as follows:
| name of medicine | Content (wt.) | CAS number | Production trade company |
| N-hydroxyphthalimides | 98.5% | 524-38-9 | Saen chemical technology (Shanghai) Co., Ltd |
| 1, 4-dioxane | ≥99.5% | 123-91-1 | SINOPHARM CHEMICAL REAGENT Co.,Ltd. |
| Beta-ionones | 97% | 14901-07-6 | Saen chemical technology (Shanghai) Co., Ltd |
And fourthly, stability test of methyl seleno glucose:
the prepared methylselenoclucose was prepared into a 3% aqueous solution, and left to stand in the air for 20 days without changing the color of the solution (fig. 1).
The aqueous selenoglucose solution prepared by the sodium borohydride reduction process developed before this subject group was exposed to air for only 3 hours, i.e., discoloration and decomposition (Ind. Eng. chem. Res. 2020, 59, 10763-10767).
Furthermore, XPS analysis of the prepared methylseleno glucose showed that selenium was present in a form having a valence of-2, as shown in FIG. 2. After the substance is prepared into an aqueous solution and exposed to the air for 31 days, the solvent is drained and then the XPS analysis is carried out, and the result shows that the selenium in the substance is not oxidized and still exists as-2-valent selenium, as shown in figure 3.
The test shows that the methyl seleno-glucose prepared by the method is more stable.
Fifthly, field experiment:
the methyl seleno-glucose prepared by the method is used as a selenium fertilizer to prepare an aqueous solution. Spraying 220mg selenium (20L water solution) per mu once in the heading and flowering stage of rice (south stalk 46). The selenium content in the rice after harvesting is detected to be 112 mug/kg (ten times average value), which meets the requirement of 40 mug/kg of selenium content of national selenium-rich rice national standard GB/T22499-.
Further, considering that the commercially available methyl grignard reagent contains methyl magnesium chloride in addition to methyl magnesium bromide and the solvent of the grignard reagent contains diethyl ether in addition to tetrahydrofuran, the methyl magnesium bromide diethyl ether solution, the methyl magnesium chloride tetrahydrofuran solution and the methyl magnesium chloride diethyl ether solution were used to synthesize the corresponding methylseleno glucose, respectively, and the above field experiments were performed, and the selenium content of the produced rice was measured to be 115 μ g/kg (ten times average), 110 μ g/kg (ten times average) and 118 μ g/kg (ten times average), respectively, similar to the above experimental data. The experimental result shows that the anions and the solvent thereof in the Grignard reagent have little influence on the performance of the prepared methylseleno glucose.
It is worth mentioning that if the selenium-substituted glucose prepared by adopting the sodium borohydride reduction process developed before the subject group is the selenium fertilizer, and the same comparison experiment is carried out, the selenium content in the rice is only 85 mug/kg (ten times of average value).
The better effect of the methyl seleno-glucose is caused by the stability of the methyl seleno-glucose, namely, the organic selenium is not easy to decompose and is more beneficial to the absorption of crops.
Sixthly, other conditions are the same as above, and the catalytic activity of the selenium carbon prepared by different glucose and methyl selenium magnesium according to the molar ratio is tested, and the result is shown in the table 1.
TABLE 1 catalytic Activity of selenium carbon materials prepared with different glucose to methyl selenium magnesium in molar ratio
Comparison table
| Number of | Molar ratio of glucose to methyl selenium magnesium | Yield of epoxy ionone product |
| 1 | 2:1 | 31% |
| 2 | 3:1 | 43% |
| 3 | 4:1 | 50% |
| 4 | 5:1 | 52% |
| 5 | 6:1 | 38% |
| 6 | 7:1 | 22% |
| 7 | 8:1 | 16% |
The above results show that the effect is best when the molar ratio of glucose to methylselenium magnesium is 5: 1.
Seventhly, the catalytic activity of the selenium carbon materials prepared by different reaction temperatures of glucose and methyl selenium magnesium is tested under the same conditions, and the results are shown in table 2.
TABLE 2 comparison of catalytic Activity of Se-carbon materials prepared at different reaction temperatures of glucose and MgSe
| Numbering | Reaction temperature | Yield of epoxy ionone product |
| 1 | 20℃ | 28% |
| 2 | 30℃ | 32% |
| 3 | 40℃ | 45% |
| 4 | 50 deg.C (example 1) | 52% |
| 5 | 60℃ | 40% |
| 6 | 70℃ | 27% |
| 7 | 90℃ | 21% |
The above results show that the solution of example 1, i.e. the reaction temperature of 50 ℃ is the most effective.
Seventhly, the other conditions are the same, the catalytic activity of the prepared selenium carbon is tested at different methyl seleno glucose calcination temperatures, and the results are shown in table 3.
TABLE 3 comparison of catalytic Activity of Se-carbon materials prepared at different methyl Seleno-glucose calcination temperatures
| Numbering | Calcination temperature | Yield of epoxy ionone product |
| 1 | 400℃ | 30% |
| 2 | 450℃ | 44% |
| 3 | 500 deg.C (example 1) | 52% |
| 5 | 550℃ | 47% |
| 6 | 600℃ | 38% |
The above results show that high temperature can destroy the structure of the selenium carbon material, resulting in reduction of catalytic activity; low temperatures are not sufficient to activate the material and likewise reduce its catalytic activity. And the best effect is achieved by adopting the calcination temperature of 500 ℃.
Claims (6)
1. A method for preparing methyl seleno-glucose and selenocarbon is characterized in that: mixing glucose and methyl selenium magnesium bromide in a solvent for reaction, wherein the solvent is anhydrous ether or tetrahydrofuran, the temperature condition of the mixing reaction of the glucose and the methyl selenium magnesium bromide is 20-80 ℃, and then evaporating the solvent to dryness to obtain the methyl seleno-glucose; mixing and grinding methyl seleno-glucose and potassium bromide, calcining in a nitrogen atmosphere at the temperature of 400-600 ℃ for 2-5 h,
and after cooling to room temperature, grinding, washing with deionized water, centrifuging to obtain a precipitate, and drying in an oven to obtain the selenium carbon.
2. The method of claim 1, wherein the methyl selenoglucose and selenocarbon are prepared by the steps of: the feeding molar ratio of the glucose to the methyl selenium magnesium bromide is 2-8: 1.
3. The method of claim 2, wherein the methyl selenoglucose and selenocarbon are prepared by the steps of: the feeding molar ratio of the glucose to the methyl selenium magnesium bromide is 5: 1.
4. The method of claim 1, wherein the methyl selenoglucose and selenocarbon are prepared by the steps of: the temperature condition of the mixing reaction of the glucose and the methyl selenium magnesium bromide is 50 ℃.
5. The method of claim 1, wherein the methyl selenoglucose and selenocarbon are prepared by the steps of: the calcining temperature environment is 500 ℃, and the calcining time is 3 h.
6. The method of claim 1, wherein the methyl selenoglucose and selenocarbon are prepared by the steps of: the mixing mass ratio of the methyl seleno-glucose to the potassium bromide is 1: 10.
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| CN113880788A (en) * | 2021-10-13 | 2022-01-04 | 上海应用技术大学 | Preparation method of 5, 6-epoxy-beta-ionone |
| CN113908861B (en) * | 2021-11-01 | 2024-04-09 | 扬州大学 | Preparation method of carbon-based selenium material and application of carbon-based selenium material in dehalogenation of dimethyl carbonate |
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Effective date of registration: 20221212 Address after: 225000 217 Development West Road, Yangzhou high tech Industrial Development Zone, Jiangsu Patentee after: YANGZHOU BANGJIE NEW MATERIAL Co.,Ltd. Address before: 225009 No. 88, South University Road, Jiangsu, Yangzhou Patentee before: YANGZHOU University |